US4518814A - Ethylene oligomeration - Google Patents
Ethylene oligomeration Download PDFInfo
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- US4518814A US4518814A US06/644,080 US64408084A US4518814A US 4518814 A US4518814 A US 4518814A US 64408084 A US64408084 A US 64408084A US 4518814 A US4518814 A US 4518814A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/20—Non-coordinating groups comprising halogens
- B01J2540/22—Non-coordinating groups comprising halogens comprising fluorine, e.g. trifluoroacetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/20—Carbonyls
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/24—Phosphines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to a novel catalyst for the oligomerization of ethylene. This invention also relates to a novel process for the oligomerization of ethylene.
- U.S. Pat. No. 3,644,564 discloses the oligomerization of ethylene in the presence of a catalyst comprising nickel(O) complexed with fluorine containing ligands.
- an object of this invention to provide an improved catalyst for the oligomerization of ethylene which is a common building block for oligomers such as higher ⁇ -olefins.
- a further object of this invention is to provide an improved process for the oligomerization of ethylene.
- This improved catalyst composition consists essentially of:
- At least one nickel compound selected from the group consisting of: bis(1,5-cyclooctadiene)nickel(O), bis(tricyclohexylphosphine)nickel(O), nickel tetracarbonyl, (cyclododecatriene)nickel, and bis(ethylene)(dicyclohexylphosphine)nickel;
- Exemplary of the phosphine compounds of the formula PR 3 are tricyclohexylphosphine, tri-n-butylphosphine, tri-isobutylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, dicyclohexylphosphine, tribenzylphosphine, ortho-tolyldiphenylphosphine, and di(ortho-tolyl)phenylphosphine, and mixtures thereof.
- Preferred is dicyclohexylphosphine.
- fluorinated carboxylic acids of the formula R'COOH for use in the present invention are trifluoroacetic acid, heptafluorobutyric acid, difluoroacetic acid, pentafluoropropionic acid, perfluoroadipic acid, and mixtures thereof. Preferred are trifluoroacetic and heptafluorobutyric.
- Exemplary dicarboxycyclic acids of the formula (R") 2 --C--(COOH) 2 are malonic acid, ethylmalonic acid, dimethylmalonic acid, benzylmalonic acid, dimethylmalonic acid, 2,2'-bis(trifluoromethyl)malonic acid, fluorotrifluoromethylmalonic acid, phthalic acid, isophthalic acid, and terephthalic acid, and mixtures thereof.
- the inventive composition is made by contacting the catalyst precursors, i.e., a suitable nickel compound, and phosphine compound, each present in a suitable solvent described in this specification, at room temperature for about 15 minutes. Subsequently the acid, present in a solvent, is added.
- the molar ratio of the phosphine ligand to the nickel compound can be broadly about 0.01-4.0 to 1, preferably about 0.5-2.5 to 1.
- the molar ratio of the particular acid used to the nickel compound should generally be about 0.01-10.0 to 1, preferably 0.05-2.0 to 1.
- ethylene is efficiently oligomerized by contacting ethylene at a temperature from about 0° C. to about 200° C. with the catalyst composition described in an earlier embodiment of the present invention, said catalyst composition being present in at least one solvent selected from the groups consisting of:
- each R v independently represents H or a C 1 to C 10 alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radical with the proviso that at least one R v is not H;
- the inventive catalyst present in at least one solvent, is prepared as described above, it is contacted with ethylene.
- the precise method of establishing ethylene/catalyst contact during the reaction is not critical.
- the catalyst system is charged to an autoclave or other similar pressure (vessel) reactor, the ethylene is introduced, and the reaction mixture is maintained with agitation at reaction temperature and pressure for the desired reaction period.
- Aromatic hydrocarbon solvents of the formula ##STR3## contemplated for use in the present invention include benzene, toluene, xylenes, trimethylbenzenes, ethylbenzenes, cumene and mixtures thereof. Toluene is presently preferred.
- Exemplary alcohols of the formula (R iv ) 3 COH include ethanol, 2-butanol, isobutanol, tertiary butanol, 2-pentanol, 1-hexanol and mixtures thereof. Preferred are 2-pentanol and tertiary butanol because they give high productivity, selectivity and ease of removal and/or recycle.
- Exemplary amides of the formula ##STR4## for use in the present invention include N,N-dimethylformamide, N,N-diphenylformamide, acetamide, N,N-dimethylacetamide, N-ethylformamide, N,N-diphenylbenzamide, benzamide and mixtures thereof. Preferred are N,N-diphenylformamide and N,N-dimethylacetamide.
- C 2 to C 20 ethers are dimethyl ether, diethyl ether, dipropyl ether, diphenyl ether, dibutyl ether, ethyl butyl ether, 1,2-dimethoxyethane and mixtures thereof. Preferred are 1,2-dimethoxyethane and diphenyl ether.
- C 2 to C 20 esters examples include ethyl acetate, propyl acetate, ethyl propionate, methyl acetate, and mixtures thereof. Ethyl acetate is preferred.
- C 3 to C 20 ketones are acetone, methyl ethyl ketone, acetophenone, 2-pentanone, 3-pentanone, 2-hexanone, cyclohexanone and mixtures thereof. Preferred are acetone and methyl ethyl ketone.
- C 2 to C 20 nitriles examples are acetonitrile, propionitrile, benzonitrile, and mixtures thereof. Preferred is acetonitrile.
- C 6 to C 20 chlorinated aromatics examples include chlorobenzene, chloroxylenes, dichlorobenzenes, chlorotoluenes, and mixtures thereof. Preferred is chlorobenzene.
- the weight ratio of the solvent employed to the combination of the nickel compound, phosphine compound and acid components can be broadly 1-10 6 to 1 with the amount of the solvent used limited only by its cost, the ease of product recovery therefrom, the required reaction vessel size, and other practical considerations.
- the preferred weight ratio is about 5-10,000 to 1.
- reaction temperatures vary from about 0° C. to 200° C., preferably from about 20° C. to 125° C.
- reaction pressure is not thought to be critical but typically varies from about 5-5000 psig, preferably from about 200-2000 psig.
- the reaction time is broadly from about 1 minute to 18 hours, preferably from about 5 minutes to 5 hours.
- the oligomerization products are separated and recovered from the reaction mixture by conventional methods such as fractional distillation, selective extraction, and adsorption.
- This example describes the generalized reaction conditions in accordance with which all the runs in Examples II-VI were carried out.
- This mixture was stirred for about 15 minutes, then the acid component to be employed was added, dissolved in a minimum volume of solvent (generally toluene).
- the reactor was then charged with ethylene to a predetermined pressure, and reaction allowed to proceed in the range of room temperature to about 80° C., heating or cooling provided as necessary.
- the reaction pressure employed varied from about 200 to about 1000 psig.
- the desired pressure was maintained by periodic incremental additions of ethylene with up to about 15 additions per run.
- the reactor was cooled to below room temperature, the ethylene pressure vented, and the reactor contents purged with nitrogen before opening the vessel.
- the resulting product mixture was weighed to determine weight gain and then filtered prior to gas liquid chromatographic (GLC) analysis.
- GLC gas liquid chromatographic
- a 150' ⁇ 0.01" glass or stainless steel capillary column coated with OV-101 was employed for sample analysis. Analysis conditions were 100° C. for two minutes after injection, followed by 32°/min temperature program up to 200° C. final column temperature.
- reaction results are reported in terms of catalyst productivity, wt % C 4 , and the % 1-olefin, % 2-olefin and % branching of the C 10 fraction.
- Catalyst productivity is defined as the grams of oligomerized (i.e. C 4 and greater) product produced per gram of Ni per hour. Productivity in some cases was calculated based on grams of ethylene reacted and in other cases was determined by comparing final weight of reactor contents with initial weight of reactor contents.
- the wt % C 4 is the wt % of C 4 of the total oligomerization product. In most reactions this was calculated from the C 10 to C 16 olefin ratios. The accuracy of this method was confirmed by trapping total product in some runs.
- Catalyst selectivity to ⁇ -olefin is measured by analyzing the C 10 fraction of the oligomerization product for 1-olefin, 2-olefin and branched C 10 olefin. Thus, these numbers represent analysis just of the C 10 fraction, with no indication of yield of the C 10 product.
- fluorinated carboxylic acids such as trifluoroacetic acid (Run 5) and heptafluorobutyric acid (Run 6) are effective catalyst components for the oligomerization of ethylene to ⁇ -olefin products compared to non-fluorinated acids (Runs 1-4).
- These fluorinated additives give very high catalyst productivities with at least half of the product mix as olefins higher than C 4 .
- a selectivity to ⁇ -olefin product of about 90% (Runs 5 and 6) is achieved as determined by analysis of the C 10 product fraction.
- the malonic acid derivatives give high catalyst productivities, with excellent selectivity to ⁇ -olefin products.
- Runs 1, 2, and 8-26 demonstrate that a variety of solvents, either alone or in admixture with a co-solvent such as toluene, are effective solvents for the oligomerization of ethylene to ⁇ -olefin products compared to solvents or admixtures which are not effective in the inventive system (Runs 3-7).
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Abstract
A novel ethylene oligomerization catalyst is provided consisting essentially of a nickel compound, a phosphine compound, and an acid. In addition, an improved ethylene oligomerization process is provided which comprises contacting ethylene with the novel catalyst composition present, in an effective solvent, at a temperature from about 0° C. to about 200° C. As a result of the inventive process, high catalyst productivity and good selectivity to desired oligomeric products are obtained.
Description
This application is a divisional of U.S. Ser. No. 490,596, filed May 2, 1983 now U.S. Pat. No. 4,482,640.
This invention relates to a novel catalyst for the oligomerization of ethylene. This invention also relates to a novel process for the oligomerization of ethylene.
A variety of catalysts, both homogeneous and heterogeneous, have been utilized to convert ethylene into olefinic products of higher molecular weight, i.e. to dimer and trimer as well as higher oligomers. For example U.S. Pat. No. 3,647,915 discloses a process for the oligomerization of ethylene employing a catalyst comprising an atom of nickel chelated with a chelating ligand having a tertiary organophosphine moiety and a carbonyl ligand. The rather complex chemical nature of the chelating ligand in U.S. Pat. No. 3,647,915 renders the use of the catalyst disclosed therein relatively expensive.
U.S. Pat. No. 3,644,564 discloses the oligomerization of ethylene in the presence of a catalyst comprising nickel(O) complexed with fluorine containing ligands.
While the catalyst systems disclosed by the above references are operable for the oligomerization of ethylene, they are merely typical of other oligomerization catalysts known in the art. By using these and other known catalyst systems for the oligomerization of ethylene, one has not always achieved high productivity of the catalyst, good selectivity to a desired oligomeric product or a combination of both.
Because of the increasing importance that oligomers are playing in the chemical industry, as exemplified by the importance of α-olefins, processes which make even slight improvements in the availability of desired oligomers over existing processes are highly desirable.
Therefore, it is an object of this invention to provide an improved catalyst for the oligomerization of ethylene which is a common building block for oligomers such as higher α-olefins. A further object of this invention is to provide an improved process for the oligomerization of ethylene.
Other aspects, objects and advantages of the present invention will become apparent from a study of this specification and the claims.
In accordance with one embodiment of the present invention, we have discovered a novel catalyst composition for the oligomerization of ethylene which is highly productive and affords good selectivity to desired oligomers. This improved catalyst composition consists essentially of:
(a) at least one nickel compound selected from the group consisting of: bis(1,5-cyclooctadiene)nickel(O), bis(tricyclohexylphosphine)nickel(O), nickel tetracarbonyl, (cyclododecatriene)nickel, and bis(ethylene)(dicyclohexylphosphine)nickel;
(b) a phosphine compound of the formula PR3 wherein R independently represents H or a C1 to C20 hydrocarbyl radical with the proviso that any alkenyl substitution be at least 3 carbon atoms removed from the phosphorus atom and at least one R is not H; and
(c) at least one acid selected from the groups consisting of:
(i) a fluorinated carboxylic acid of the formula R'COOH wherein R' represents a C1 to C10 hydrocarbyl radical having at least 1 fluorine (F) atom;
(ii) a dicarboxylic acid of the formula (R")2 --X--(COOH)2 wherein R" independently represents H or a C1 to C20 hydrocarbyl or fluorinated hydrocarbyl radical, and X is a tetravalent C atom or the tetra-substituted benzene radical C6 H2 ;
(iii) 2-ketobutyric acid; and
(iv) glycine.
Exemplary of the phosphine compounds of the formula PR3 are tricyclohexylphosphine, tri-n-butylphosphine, tri-isobutylphosphine, dicyclohexylphenylphosphine, diethylphenylphosphine, dicyclohexylphosphine, tribenzylphosphine, ortho-tolyldiphenylphosphine, and di(ortho-tolyl)phenylphosphine, and mixtures thereof. Preferred is dicyclohexylphosphine.
Examples of fluorinated carboxylic acids of the formula R'COOH for use in the present invention are trifluoroacetic acid, heptafluorobutyric acid, difluoroacetic acid, pentafluoropropionic acid, perfluoroadipic acid, and mixtures thereof. Preferred are trifluoroacetic and heptafluorobutyric.
Exemplary dicarboxycyclic acids of the formula (R")2 --C--(COOH)2 are malonic acid, ethylmalonic acid, dimethylmalonic acid, benzylmalonic acid, dimethylmalonic acid, 2,2'-bis(trifluoromethyl)malonic acid, fluorotrifluoromethylmalonic acid, phthalic acid, isophthalic acid, and terephthalic acid, and mixtures thereof. Preferred are benzylmalonic acid and dimethylmalonic acid.
While the order of addition of catalyst precursors is not thought to be critical in the present invention, preferably the inventive composition is made by contacting the catalyst precursors, i.e., a suitable nickel compound, and phosphine compound, each present in a suitable solvent described in this specification, at room temperature for about 15 minutes. Subsequently the acid, present in a solvent, is added.
In the catalyst composition, the molar ratio of the phosphine ligand to the nickel compound can be broadly about 0.01-4.0 to 1, preferably about 0.5-2.5 to 1. The molar ratio of the particular acid used to the nickel compound should generally be about 0.01-10.0 to 1, preferably 0.05-2.0 to 1.
In accordance with another embodiment of the present invention we have discovered that ethylene is efficiently oligomerized by contacting ethylene at a temperature from about 0° C. to about 200° C. with the catalyst composition described in an earlier embodiment of the present invention, said catalyst composition being present in at least one solvent selected from the groups consisting of:
(i) an aromatic hydrocarbon of the formula ##STR1## wherein R"' represents a C1 to C6 alkyl radical and n is 0, 1, 2, 3, or 4;
(ii) an alcohol of the formula (Riv)3 COH wherein Riv independently represents H or a C1 to C12 alkyl, cycloalkyl, aryl, alkaryl, or aralkyl radical with the proviso that at least one Riv is not hydrogen;
(iii) an amide of the formula ##STR2## wherein each Rv independently represents H or a C1 to C10 alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radical with the proviso that at least one Rv is not H;
(iv) a C2 to C20 ether;
(v) a C2 to C20 ester;
(vi) a C3 to C20 ketone;
(vii) a C2 to C20 nitrile; and;
(viii) a C6 to C20 chlorinated aromatic.
After the inventive catalyst, present in at least one solvent, is prepared as described above, it is contacted with ethylene. The precise method of establishing ethylene/catalyst contact during the reaction is not critical. In one modification, the catalyst system is charged to an autoclave or other similar pressure (vessel) reactor, the ethylene is introduced, and the reaction mixture is maintained with agitation at reaction temperature and pressure for the desired reaction period.
Aromatic hydrocarbon solvents of the formula ##STR3## contemplated for use in the present invention include benzene, toluene, xylenes, trimethylbenzenes, ethylbenzenes, cumene and mixtures thereof. Toluene is presently preferred.
Exemplary alcohols of the formula (Riv)3 COH include ethanol, 2-butanol, isobutanol, tertiary butanol, 2-pentanol, 1-hexanol and mixtures thereof. Preferred are 2-pentanol and tertiary butanol because they give high productivity, selectivity and ease of removal and/or recycle.
Exemplary amides of the formula ##STR4## for use in the present invention include N,N-dimethylformamide, N,N-diphenylformamide, acetamide, N,N-dimethylacetamide, N-ethylformamide, N,N-diphenylbenzamide, benzamide and mixtures thereof. Preferred are N,N-diphenylformamide and N,N-dimethylacetamide.
Examples of C2 to C20 ethers are dimethyl ether, diethyl ether, dipropyl ether, diphenyl ether, dibutyl ether, ethyl butyl ether, 1,2-dimethoxyethane and mixtures thereof. Preferred are 1,2-dimethoxyethane and diphenyl ether.
Examples of C2 to C20 esters include ethyl acetate, propyl acetate, ethyl propionate, methyl acetate, and mixtures thereof. Ethyl acetate is preferred.
Examples of C3 to C20 ketones are acetone, methyl ethyl ketone, acetophenone, 2-pentanone, 3-pentanone, 2-hexanone, cyclohexanone and mixtures thereof. Preferred are acetone and methyl ethyl ketone.
Examples of C2 to C20 nitriles are acetonitrile, propionitrile, benzonitrile, and mixtures thereof. Preferred is acetonitrile.
Examples of C6 to C20 chlorinated aromatics include chlorobenzene, chloroxylenes, dichlorobenzenes, chlorotoluenes, and mixtures thereof. Preferred is chlorobenzene.
Whatever solvent is used, of course, must exist as a liquid at oligomerization reaction conditions.
The weight ratio of the solvent employed to the combination of the nickel compound, phosphine compound and acid components can be broadly 1-106 to 1 with the amount of the solvent used limited only by its cost, the ease of product recovery therefrom, the required reaction vessel size, and other practical considerations. The preferred weight ratio is about 5-10,000 to 1.
Broadly, reaction temperatures vary from about 0° C. to 200° C., preferably from about 20° C. to 125° C.
The reaction pressure is not thought to be critical but typically varies from about 5-5000 psig, preferably from about 200-2000 psig.
The reaction time is broadly from about 1 minute to 18 hours, preferably from about 5 minutes to 5 hours.
The oligomerization products are separated and recovered from the reaction mixture by conventional methods such as fractional distillation, selective extraction, and adsorption.
It is within the scope of this invention to employ a batchwise or continuous reaction system wherein ethylene is passed in a continuous manner into a reaction zone containing the inventive catalyst system while ethylene oligomerization product mixture is concomitantly withdrawn from the reaction mixture.
The following examples further illustrate the present invention.
This example describes the generalized reaction conditions in accordance with which all the runs in Examples II-VI were carried out.
All runs described in Examples II-VI were carried out in a 300 mL stainless steel (316SS) Autoclave Engineers stirred tank reactor. The reactor was first charged with 50 mL of solvent, sealed under nitrogen, then pressured with ethylene and vented to aid oxygen removal. Under a sweep of ethylene, 0.5 g of bis(1,5-cyclooctadiene)nickel(O) (Ni(O)COD) was added, in a minimum volume of solvent (generally toluene). Then, the desired amount of a phosphine compound was added, dissolved in a minimum volume of solvent (generally toluene). This mixture was stirred for about 15 minutes, then the acid component to be employed was added, dissolved in a minimum volume of solvent (generally toluene). The reactor was then charged with ethylene to a predetermined pressure, and reaction allowed to proceed in the range of room temperature to about 80° C., heating or cooling provided as necessary. The reaction pressure employed varied from about 200 to about 1000 psig. The desired pressure was maintained by periodic incremental additions of ethylene with up to about 15 additions per run. When the reaction was complete, the reactor was cooled to below room temperature, the ethylene pressure vented, and the reactor contents purged with nitrogen before opening the vessel.
The resulting product mixture was weighed to determine weight gain and then filtered prior to gas liquid chromatographic (GLC) analysis. A 150'×0.01" glass or stainless steel capillary column coated with OV-101 was employed for sample analysis. Analysis conditions were 100° C. for two minutes after injection, followed by 32°/min temperature program up to 200° C. final column temperature.
In the following examples, reaction results are reported in terms of catalyst productivity, wt % C4, and the % 1-olefin, % 2-olefin and % branching of the C10 fraction. Catalyst productivity is defined as the grams of oligomerized (i.e. C4 and greater) product produced per gram of Ni per hour. Productivity in some cases was calculated based on grams of ethylene reacted and in other cases was determined by comparing final weight of reactor contents with initial weight of reactor contents. The wt % C4 is the wt % of C4 of the total oligomerization product. In most reactions this was calculated from the C10 to C16 olefin ratios. The accuracy of this method was confirmed by trapping total product in some runs. Catalyst selectivity to α-olefin is measured by analyzing the C10 fraction of the oligomerization product for 1-olefin, 2-olefin and branched C10 olefin. Thus, these numbers represent analysis just of the C10 fraction, with no indication of yield of the C10 product.
A series of runs were carried out in 2-pentanol as solvent, with bis(1,5-cyclooctadiene)nickel(O) [Ni(O)COD], dicyclohexylphosphine [DCHP] and a variety of monocarboxylic acids, following the general procedure described above. Thus, 50 mL of 2-pentanol and reagents as listed in Table I were charged to the reactor. Reaction parameters and results are summarized in Table I.
TABLE I
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Reaction Parameters
Reagents, mmol Time,
Temp,
Press, Wt %
C-10 fraction, wt %
Run
Acid Ni(COD)
DCHP
min.
°C.
psig
Productivity
C.sub.4
1-olefin
2-olefin
Branching
__________________________________________________________________________
1 None 1.82 1.87
240 50 850 Trace
2 CH.sub.3 CO.sub.2 H,
0.83
1.93 1.97
150 50 850 Trace
3 CH.sub.2 ClCO.sub.2 H,
2.0
2.04 1.92
150 35 650 40 63 55 25 20
4 CCl.sub.3 CO.sub.2 H,
1.8
1.85 1.82
175 50 800 Trace
5 CF.sub.3 CO.sub.2 H,
0.96
1.89 1.92
80 55 600 700 42 90 7 4
6 Heptafluorobutyric,
1.9
1.85 1.87
42 55 700 1860 50 90 5 5
__________________________________________________________________________
The above data demonstrate that fluorinated carboxylic acids such as trifluoroacetic acid (Run 5) and heptafluorobutyric acid (Run 6) are effective catalyst components for the oligomerization of ethylene to α-olefin products compared to non-fluorinated acids (Runs 1-4). These fluorinated additives give very high catalyst productivities with at least half of the product mix as olefins higher than C4. A selectivity to α-olefin product of about 90% (Runs 5 and 6) is achieved as determined by analysis of the C10 product fraction.
A series of runs were carried out in 2-pentanol solvent, with Ni(O)COD, DCHP and a variety of dicarboxylic acids, following the general procedure described above in Example I. Thus, 50 mL of 2-pentanol and reagents as listed in Table II were charged to the reactor. Reaction parameters and results are summarized in Table II.
TABLE II
__________________________________________________________________________
Reaction Parameters
Reagents, mmol Time,
Temp, Press, Wt %
C-10 fraction, wt %
Run
Acid Ni(COD)
DCHP
min.
°C.
psig
Productivity
C.sub.4
1-olefin
2-olefin
Branching
__________________________________________________________________________
1 None 1.82 1.87
240 50 850 Trace
2 Oxalic, 1.3
1.93 1.92
180 50 800 Trace
3 Adipic, 1.0
2.0 1.97
165 50 850 20 Trace
(1) Malonic acid derivatives:
4 Et Malonic,
1.7
1.64 1.67
150 55 700 340 30 93 5 3
5 Benzyl Malonic,
1.6
1.67 1.67
150 60 700 530 34 90 7 4
6 Me.sub.2 Malonic,
1.7
1.78 1.82
120 60 700 340 27 95 4 2
7 Me.sub.2 Malonic,
1.9
1.89 1.87
210 55 700 290 26 95 3 2
8 Me.sub.2 Malonic,
1.7
1.67 1.67
150 55 700 320 30 95 3 2
9 Me.sub.2 Malonic,
1.9
1.93 1.92
175 55 700 320 21 95 4 2
10 Me.sub.2 Malonic,
2.0
2.07 2.07
140 55 700 270 27 94 4 2
11 Et.sub.2 Malonic,
2.0
2.00 1.97
115 55 700 150 66 91 5 4
(2) Aromatic dicarboxylic acids:
12 Terephthalic,
0.9
1.75 1.77
320 55 700 70 26 93 5 2
13 Phthalic,
0.9
1.75 1.82
250 35 600 70 62 93 2 5
14 Isophthalic,
1.0
2.22 2.27
230 45 750 60 30 90 8 2
__________________________________________________________________________
The data demonstrate that dicarboxylic acids such as the malonic acid derivatives studied in runs 4-11 and the aromatic derivatives studied in runs 12-14 are effective catalyst components for the oligomerization of ethylene to α-olefin products compared to the presence of either no acid additive (Run 1) or additives which are not part of the inventive system (Runs 2 and 3). The malonic acid derivatives give high catalyst productivities, with excellent selectivity to α-olefin products. The aromatic diacids, while giving lower catalyst productivities than the malonic acid derivatives, give excellent selectivities to α-olefin products.
Several runs were carried out in 2-pentanol solvent, with Ni(O)COD, DCHP and a variety of polyfunctional acids, following the general procedure set forth above. Thus, 50 mL of 2-pentanol and reagents as listed in Table III were charged to the reactor. Reaction parameters and results are summarized in Table III.
TABLE III
__________________________________________________________________________
Reaction Parameters
Reagents, mmol Time,
Temp,
Press, Wt %
C-10 fraction, wt %
Run
Acid Ni(COD)
DCHP
min.
°C.
psig
Productivity
C.sub.4
1-olefin
2-olefin
Branching
__________________________________________________________________________
1 None 1.82 1.87
240 50 850 Trace
2 3-hydroxybutyric,
1.7
1.75 1.77
130 55 800 30 56 89 3 8
3 4-acetylbutyric,
1.9
1.93 1.87
125 50 750 20 63 98 2 tr
4 DL-α-hydroxycaproic,
1.9
1.89 1.87
130 50 850 20 70 63 21 16
5 2-Ketobutyric,
1.9
1.85 1.87
140 50 760 50 6 95 0 5
6 Glycine, 1.5
1.53 1.52
120 55 875 130 38 96 3 1
__________________________________________________________________________
The data demonstrate that the polyfunctional acids 2-ketobutyric acid (Run 5) and glycine (Run 6) are effective catalyst components for the oligomerization of ethylene to α-olefin products. 2-Ketobutyric acid shows greater than 90% selectivity for oligomers higher than C4, with excellent selectivity to α-olefin product. Essentially no olefin isomerization, as measured by production of α- and β-olefin in the C10 fraction, is observed, while only low levels of branched oligomers are observed. Glycine demonstrates surprisingly high catalyst productivity when compared to the other polyfunctional acids studied. In addition, glycine gives greater than 95% selectivity to α-olefin product, with only low levels of β-olefin and branched olefin observed.
A series of runs were carried out in accordance with the general procedure described above. Thus, 50 mL of toluene, Ni(O)COD, trifluoroacetic acid (TFA) and a variety of phosphines were charged to the reactor. Reaction parameters and results are summarized in Table IV.
TABLE IV
__________________________________________________________________________
Reaction Parameters
Reagents, mmol Time,
Temp.,
Press, Wt %
C-10 fraction, wt %
Run
Phosphine Ni(COD)
TFA
min.
°C.
psig
Productivity
C.sub.4
1-olefin
2-olefin
Branching
__________________________________________________________________________
##STR5## 1.9
1.93 1.93
120 50 300 250 18 32 59 9
2
(PhCH.sub.2).sub.3 P,
1.8
1.82 1.84
55 50 500 1480 56 51 22 27
3
##STR6## 1.7
1.64 1.67
75 55 500 880 21 69 23 8
4
PhEt.sub.2 P,
1.5
1.75 1.75
110 54 300 360 57 70 11 19
5
##STR7## 1.8
1.82 1.84
100 50 300 490 63 43 20 37
6
##STR8## 1.9
1.93 1.93
90 50 300 720 33 64 26 10
7
##STR9## 1.6
1.75 1.67
90 50 400 410 51 48 32 20
8
##STR10##
1.9
1.96 1.93
90 50 300 750 50 15 8 77
__________________________________________________________________________
The above data demonstrate that a variety of simple phosphines are effective catalyst components for the oligomerization of ethylene to α-olefin products. High catalyst productivities are achieved in all instances with good selectivities to α-olefin except in Run 8.
A series of runs were carried out in a variety of solvents, employing 50 mL of total solvent in each run, either as pure solvent or in admixture with toluene. In all runs, Ni(O)COD,DCHP, and TFA were added dissolved in about 10 mL of additional toluene. Amounts of reagents charged, reaction parameters and results are presented in Table V.
TABLE V
__________________________________________________________________________
Reaction Parameters
Reagents, mmol
Time,
Temp,
Press, Wt %
C-10 fraction, wt %
Run
Solvent Ni(COD)
DCHP
TFA
min.
°C.
psig
Productivity
C.sub.4
1-olefin
2-olefin
Branching
__________________________________________________________________________
1 Toluene 1.63 1.67
1.67
75 54 500 880 21 69 23 8
2 Toluene 1.82 1.77
1.75
50 60 700 1360 23 69 24 7
3 40 mL Toluene
2.15 2.12
2.11
140 47 875 10 trace
10 g formamide
4 40 mL Toluene/
1.71 1.67
1.67
140 55 700 90 41 67 25 8
10 g HMPA
5 Formamide 1.78 1.72
1.75
150 50 700 10 trace
6 Methanol 2.00 2.00
2.00
180 63 400 260 80 43 22 35
7 40 mL Toluene/
1.75 1.77
1.75
180 54 800 trace
morpholine
8 40 mL Toluene/
1.74 1.82
1.75
190 52 700 260 34 84 10 6
10 mL N,N--DMF
9 40 mL Toluene/
1.67 1.72
1.67
60 55 700 1390 30 74 20 6
10 g diphenyl-
formamide
10 40 mL Toluene/
1.64 1.72
1.67
120 54 700 380 36 63 32 6
10 g acetamide
11 40 mL Toluene/
1.89 1.92
1.93
110 55 700 540 29 79 14 7
10 mL dimethyl-
acetamide
12 40 mL Toluene/
1.93 1.97
1.93
110 58 700 900 27 70 23 8
10 g phthalimide
13 N,N--DMF 2.11 2.17
2.11
175 54 700 140 60 86 7 7
14 N,N--Dimethyl-
1.67 1.67
1.67
170 55 700 200 50 78 12 10
acetamide
15 EtOH 1.89 1.82
1.93
100 53 500 290 72 77 5 18
16 s-BuOH 2.00 2.02
2.02
130 55 500 210 54 88 6 7
17 i-BuOH 1.96 2.02
1.93
210 66 500 260 70 67 17 16
18 t-BuOH 1.89 1.97
1.93
95 57 500 520 36 89 6 6
19 2-C.sub.5 OH
1.89 1.92
0.96
80 55 600 700 43 90 7 4
20 40 mL Toluene/
1.78 1.87
1.75
100 60 700 770 41 78 12 10
10 mL Ph.sub.2 O
21 40 mL Toluene/
1.85 1.82
1.84
75 55 700 1130 23 71 22 7
10 mL DME*
22 40 mL Toluene/
2.00 2.07
2.01
100 57 700 770 58 73 19 8
10 mL CH.sub.3 CN
23 40 mL Toluene/
1.85 1.92
1.84
45 55 700 1400 28 76 17 7
10 mL acetone
24 40 mL Toluene/
1.89 1.82
1.93
50 55 700 2140 32 75 17 8
10 mL MEK
25 40 mL Toluene/
1.82 1.77
1.84
50 55 700 1720 32 73 18 9
10 mL EtOAc
26 40 mL Toluene/
1.75 1.82
1.75
50 53 700 2550 29 74 18 9
10 mL PhCl
__________________________________________________________________________
*1,2-dimethoxyethane
The results of Runs 1, 2, and 8-26 demonstrate that a variety of solvents, either alone or in admixture with a co-solvent such as toluene, are effective solvents for the oligomerization of ethylene to α-olefin products compared to solvents or admixtures which are not effective in the inventive system (Runs 3-7).
Catalyst productivities as high as 2500 g of oligomer/g Ni/hr are achieved (see run 26; PhCl solvent) and high selectivities to α-olefin products are possible using such solvents as t-butanol and 2-pentanol (see runs 18 and 19). In addition, by appropriate choice of solvent, varying levels of C4 versus higher oligomers can be obtained--compare Runs 15 (72%) and 21 (23%), for example.
Reasonable variations and modifications are possible within the scope of the foregoing.
Claims (6)
1. An improved process for the oligomerization of ethylene comprising contacting said ethylene with a catalyst composition in the liquid phase present in at least one solvent selected from the groups consisting of:
(i) an aromatic hydrocarbon of the formula ##STR11## wherein R"' represents a C1 to C6 alkyl radical and n is 0, 1, 2, 3, or 4;
(ii) an alcohol of the formula (Riv)3 COH wherein Riv independently represents H or a C1 to C12 alkyl, cycloalkyl, aryl, alkaryl, or aralkyl radical with the proviso that at least one Riv is not hydrogen;
(iii) an amide of the formula ##STR12## wherein each Rv independently represents H or a C1 to C10 alkyl, cycloalkyl, aryl, aralkyl, or alkaryl radical with the proviso that at least one Rv is not H;
(iv) a C2 to C20 ether;
(v) a C2 to C20 ester;
(vi) a C3 to C20 ketone;
(vii) a C2 to C20 nitrile; and
(viii) a C6 to C20 chlorinated aromatic, the catalyst consisting essentially of:
(a) at least one nickel compound selected from the group consisting of:
bis(1,5-cyclooctadiene)nickel(O);
bis(tricyclohexylphosphine)nickel(O);
nickel tetracarbonyl;
(cyclododecatriene)nickel; and
bis(ethylene)(dicyclohexylphosphine)nickel;
(b) a phosphine compound of the formula PR3 wherein R independently represents H or a C1 to C20 hydrocarbyl radical with the proviso that any alkenyl substitution be at least 3 carbon atoms removed from the phosphorus atom and at least one R is not H; and
(c) an acid selected from the group consisting of (i) a fluorinated carboxcyclic acid of the formula R'COOH wherein R' represents a C1 to C10 hydrocarbyl radical having at least 1 fluorine (F) atom, (ii) a dicarboxcyclic acid of the formula (R")2 --X--(COOH)2 wherein R" independently represents H or a C1 to C20 hydrocarbyl or fluorinated hydrocarbyl radical and X is a tetravalent C atom or the tetra-substituted benzene radical C6 H2 ; (iii) 2-ketobutyric acid and (iv) glycine, such that the molar ratio of (b) to (a) is about 0.01-4.0 to 1 and the molar ratio of (c) to (a) is about 0.01-10.0 to 1 at a temperature of from about 0° C. to about 200° C.
2. A process according to claim 1 carried out at a temperature of from about 20° C. to about 125° C.
3. A process according to claim 1 wherein said solvent is toluene.
4. A process according to claim 1 wherein said solvent is one selected from the group consisting of ethanol, sec-butanol, t-butanol, iso-butanol and 2-butanol, and 2-hexanol.
5. A process according to claim 3 wherein said solvent consists of toluene and at least one selected from the group consisting of N,N-dimethylformamide, diphenylformamide, acetamide, dimethyl acetamide, and phthalimide.
6. A process according to claim 3 wherein said solvent consists of toluene and at least one selected from the group consisting of diphenyl ether, 1,2-dimethoxyethane, acetonitrile, acetone, methyl ethyl ketone, ethyl acetate, and chlorobenzene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/644,080 US4518814A (en) | 1983-05-02 | 1984-08-24 | Ethylene oligomeration |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/490,596 US4482640A (en) | 1983-05-02 | 1983-05-02 | Ethylene oligomerization |
| US06/644,080 US4518814A (en) | 1983-05-02 | 1984-08-24 | Ethylene oligomeration |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/490,596 Division US4482640A (en) | 1983-05-02 | 1983-05-02 | Ethylene oligomerization |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4518814A true US4518814A (en) | 1985-05-21 |
Family
ID=27050100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/644,080 Expired - Lifetime US4518814A (en) | 1983-05-02 | 1984-08-24 | Ethylene oligomeration |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4634793A (en) * | 1984-11-09 | 1987-01-06 | Shell Oil Company | Process for the dimerization of olefins |
| US4717785A (en) * | 1986-12-10 | 1988-01-05 | Shell Oil Company | Removal of phosphine impurities from higher olefins |
| US4806647A (en) * | 1987-02-24 | 1989-02-21 | Shell Oil Company | Process for the dimerization of olefins |
| US5130458A (en) * | 1991-10-29 | 1992-07-14 | Phillips Petroleum Company | Preparation of bis(1,5-cyclooctadiene)nickel(O) |
| US5162595A (en) * | 1991-12-18 | 1992-11-10 | Phillips Petroleum Company | Ethylene dimerization |
| US5221774A (en) * | 1992-03-19 | 1993-06-22 | Phillips Petroleum Company | Ethylene oligomerization |
| US5237118A (en) * | 1992-08-21 | 1993-08-17 | Phillips Petroleum Company | Ethylene oligomerization |
| US5245097A (en) * | 1991-12-18 | 1993-09-14 | Phillips Petroleum Company | Ethylene oligomerization |
| US5272124A (en) * | 1992-11-20 | 1993-12-21 | Phillips Petroleum Company | Ethylene polymerization catalyst comprising a nickel compound and an aromatic carboxylic acid compound |
| US5658494A (en) * | 1992-02-14 | 1997-08-19 | Amersham International Plc | Fluorescent compounds |
| US6184428B1 (en) | 1998-04-22 | 2001-02-06 | Saudi Basic Industries Corporation | Catalyst and process for ethylene oligomerization |
| US10308563B2 (en) * | 2016-12-15 | 2019-06-04 | Hanwha Total Petrochemical Co., Ltd. | Process for producing ethylene oligomers |
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|---|---|---|---|---|
| US4634793A (en) * | 1984-11-09 | 1987-01-06 | Shell Oil Company | Process for the dimerization of olefins |
| US4717785A (en) * | 1986-12-10 | 1988-01-05 | Shell Oil Company | Removal of phosphine impurities from higher olefins |
| US4806647A (en) * | 1987-02-24 | 1989-02-21 | Shell Oil Company | Process for the dimerization of olefins |
| US4859646A (en) * | 1987-02-24 | 1989-08-22 | Shell Oil Company | Process for the dimerization of olefins |
| US5130458A (en) * | 1991-10-29 | 1992-07-14 | Phillips Petroleum Company | Preparation of bis(1,5-cyclooctadiene)nickel(O) |
| US5245097A (en) * | 1991-12-18 | 1993-09-14 | Phillips Petroleum Company | Ethylene oligomerization |
| US5162595A (en) * | 1991-12-18 | 1992-11-10 | Phillips Petroleum Company | Ethylene dimerization |
| US5658494A (en) * | 1992-02-14 | 1997-08-19 | Amersham International Plc | Fluorescent compounds |
| US5221774A (en) * | 1992-03-19 | 1993-06-22 | Phillips Petroleum Company | Ethylene oligomerization |
| US5237118A (en) * | 1992-08-21 | 1993-08-17 | Phillips Petroleum Company | Ethylene oligomerization |
| US5272124A (en) * | 1992-11-20 | 1993-12-21 | Phillips Petroleum Company | Ethylene polymerization catalyst comprising a nickel compound and an aromatic carboxylic acid compound |
| US5322910A (en) * | 1992-11-20 | 1994-06-21 | Phillips Petroleum Company | Ethylene polymerization |
| US6184428B1 (en) | 1998-04-22 | 2001-02-06 | Saudi Basic Industries Corporation | Catalyst and process for ethylene oligomerization |
| US10308563B2 (en) * | 2016-12-15 | 2019-06-04 | Hanwha Total Petrochemical Co., Ltd. | Process for producing ethylene oligomers |
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